Laboratory Experiment

pubs.acs.org/jchemeduc

A Simple ZnO Nanocrystal Synthesis Illustrating Three-Dimensional

Quantum Confinement
Philip J. Reid,* Bryant Fujimoto, and Daniel R. Gamelin
Department of Chemistry, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States
*
S Supporting Information

ABSTRACT: Semiconductor nanocrystals or “quantum dots” are attractive materials for

exploring quantum confinement effects. For example, band-gap energies of these
materials depend on particle size, and this dependence can be explained using simple,
quantum mechanical models. We outline here an undergraduate physical chemistry
laboratory involving the room-temperature synthesis and absorption spectroscopy of
ZnO nanocrystals. The experimental results are compared with the predictions of a
three-dimensional quantum confinement (or “particle-in-a-sphere”) model. The ease of
synthesis and data collection, the common precursors employed, and the simple
spectroscopic analysis allow facile incorporation of this experiment into essentially any
undergraduate laboratory program.

KEYWORDS: Upper-Division Undergraduate, Inorganic Chemistry, Laboratory Instruction, Physical Chemistry,

Hands-On Learning/Manipulatives, Interdisciplinary/Multidisciplinary, Nanotechnology, Quantum Chemistry, UV-Vis Spectroscopy

T he remarkable growth in materials chemistry over the past

two decades has increased the need to explore this area in
undergraduate chemistry curricula. One class of materials that
has received substantial interest is semiconductor nanocrystals,
or “quantum dots”. These materials have a wide range of
potential applications including single-particle imaging, particle
tracking, and photovoltaics.1−4 Semiconductor nanocrystals are
also fundamentally interesting materials in that their electronic
properties depend on particle size.5,6 Specifically, the difference
in energy between the valence and conduction band edges, or
“band gap”, of the nanocrystal depends on its size, with a
decrease in particle size increasing the band-gap energy. These
so-called quantum confinement effects can be described using
relatively simple “particle-in-a-box” quantum-mechanical mod-
els. Therefore, semiconductor nanocrystals are an excellent
venue in which to explore foundational quantum-mechanical
ideas in a modern context.
A variety of laboratory experiments have been presented in
which students synthesize the quantum dots and then analyze
their properties.7,8 Early experiments focused on CdS and CdSe
relative ease of preparation makes these particles an attractive
target for study.10−13
The laboratory described here involves ZnO nanocrystal
syntheses involving common precursors where the growth
kinetics are sufficiently fast that particle growth can be studied
within a three-hour lab period.14 Here, solutions of zinc acetate
and tetramethyl ammonium hydroxide in ethanol are prepared
and mixed, and particle growth at room temperature is
monitored using UV−Vis absorption spectroscopy. The
lowest-energy electronic transition provides a measure of the
band-gap energy, which evolves as the particles grow in size.
The change in band-gap energy with particle size is measured
and compared to predictions of the “particle-in-a-sphere”
model. All of the reagents used in this lab are easily acquired,
and the entire experiment is performed at room temperature
with the majority of particle growth evident in ∼30 min. This
experiment provides a simple, robust way to incorporate
modern materials chemistry and quantum mechanics into the
undergraduate laboratory curriculum.

quantum dots, but these laboratories involved syntheses that
employed relatively toxic compounds (in particular, Cd
precursors) and high temperatures.8,9 CdS and CdSe quantum
dots are now commercially available, so synthesis of these
materials can be avoided altogether.9 However, the relative ease
of nanoparticle synthesis is pedagogically attractive aspect of
nanocrystal experiments. An alternative is to study materials
where synthetic precursors are significantly less toxic than those
employed for CdS or CdSe. In particular, ZnO quantum dots
have emerged as an “experimentally friendly” material, and their
© 2013 American Chemical Society and
Division of Chemical Education, Inc.
■
THEORY
The simplest quantum-confinement model is the particle in a
one-dimensional box.15 In this model, the particle is subjected
to a constraining potential resulting in its confinement to the
region of 0 ≤ x ≤ lx where lx is the “length of the box”.15 The
available energy levels (En) are given by
Published: December 9, 2013
280 dx.doi.org/10.1021/ed300693d | J. Chem. Educ. 2014, 91, 280−282
Journal of Chemical Education Laboratory Experiment

n2ℏ2π 2 dehydrate, Zn(C2H3O2)2·2H2O, with tetramethyl ammonium

En =
2lx2 (1)
The energy levels are quantized, indexed by n where n = 1, 2, ...,
∞. The model also predicts that the energy levels depend on
the length of the box as En ∝ 1/l2x. A long-standing experiment
in physical chemistry laboratories is the application of this
model to describe the absorption spectra of conjugated
alkenes.16 The electrons residing in the π-conjugated orbitals
are treated as residing in a box defined by the conjugation, and
a study of conjugated molecules of varying length is performed
to test the validity this model.
For semiconductor nanocrystals, a three-dimensional (3D)
version of the particle-in-a-box model is used to describe the
change in energy levels with particle size. In semiconductors,
hydroxide pentahydrate, N(CH4)4OH·5H2O. Approximately
0.03 g of Zn(C2H3O2)2·2H2O (98% purity, Sigma-Aldrich) is
dissolved in 7 mL of ethanol (200 proof, Decon Labs). A
tetramethyl ammonium hydroxide solution is made by
dissolving 0.07 g of N(CH4)4OH·5H2O (97%, Sigma-Aldrich)
in 7 mL of ethanol. Formation of the ZnO nanoparticles is
initiated by adding 0.10 mL of the tetramethyl ammonium
hydroxide solution to a fused silica cuvette containing 0.25 mL
of the zinc acetate solution and 1 mL of ethanol. The growth of
ZnO nanoparticles is monitored by measuring the UV−vis
absorption spectrum from 230 to 390 nm as a function of time.
Absorption spectra are acquired 1, 2, 4, 8, 16, and 32 min after
initiation of the reaction. The solution is transferred from the
cuvette to a sealed vial where it was held for two days after
which a final absorption spectrum is measured.

■
absorption of a photon promotes an electron from the valence
band to the conduction band, leaving a “hole” in the valence
band. The electron−hole pair is referred to as an exciton. In the HAZARDS
bulk, the electron and hole occupy a volume characterized by Safety goggles should be worn at all times during the
the exciton Bohr radius, which depends on the electronic experiment. Ethanol is flammable and should not be used
structure and dielectric constant of the semiconductor. For around open flames. Tetramethyl ammonium hydroxide is
example, this radius is 56 Å for CdSe9 and 24 Å for ZnO.12 highly toxic by ingestion, and somewhat toxic by skin
When the nanocrystal radius is comparable to the Bohr radius, absorption. Disposable gloves should be worn when handling
confinement effects are observed corresponding to an increase this material. Zinc acetate is reactive with oxidizing agents.
in the band gap energy. The confinement of an electron (or
hole) in the nanocrystal can be modeled assuming spherical
symmetry, or the “particle-in-a-sphere” model. In spherical
■ RESULTS
The absorption spectrum of the ZnO nanoparticle solution as a
polar coordinates, the time-independent Schrodinger equation function of time is shown in Figure 1. After 1 min, a transition
is
ℏ2 ⎛ ∂ 2 2 ∂⎞ 1 ̂2
− ⎜ 2 + ⎟ψ (r , θ , ϕ) + L ψ (r , θ , ϕ)
2m ⎝ ∂r r ∂r ⎠ 2mr
+ V (r )ψ (r , θ , ϕ) = Eψ (r , θ , ϕ) (2)
The potential energy term is defined as V(r) = 0 when the
particle is inside the sphere of radius a (0 ≤r ≤ a) and V(r) =
∞ everywhere else. The band gap energy derived from this
model depends on the nanocrystal radius (R):8,13
ℏ2π 2 ⎛ 1 1 ⎞
bulk
E bg = E bg + ⎜ + ⎟
2R2 ⎝ me* mh* ⎠ (3)
Here, Ebg is band-gap energy of a nanocrystal with radius R,
eg is the band-gap energy of the bulk semiconductor, and m*
Ebulk e
and m*h are the electron and hole effective masses. Due to
dielectric screening, the electron and hole effective masses are
smaller than that of a free electron. Because the photogenerated Figure 1. UV−vis absorption spectra collected during of ZnO
electron and hole have opposite charges, they attract one nanocrystal growth. Spectra were taken at various times after initiation
another via Coulomb interaction such that the band-gap energy of the reaction as indicated. The lowest-energy absorption band
of the semiconductor is less than expected from eq 3. This provides a measure of the band-gap energy.
stabilization is referred to as the exciton binding energy, and a
correction term is added to eq 4 to account for this effect:
ℏ2π 2 ⎛ 1 1 ⎞ 1.8e 2 centered at ∼290 nm is observed corresponding to the band
bulk
E bg = E bg + ⎜ + ⎟ −
2R2 ⎝ me* mh* ⎠ 4πεε0R (4) gap of the semiconductor. As the particles grow, this transition
shifts to longer wavelengths (lower energy) ultimately reaching
Here, ε is the dielectric constant of the semiconductor and ε0 is ∼340 nm in 48 h.
the vacuum permittivity. The central prediction of eq 5 is that Data analysis involves determining the band-gap energy from
the band-gap energy should scale as 1/R2.

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the electronic absorption spectrum by identifying the wave-
length at which the rising edge of the absorption band edge is
EXPERIMENT half of the bend maximum (λhalf) and converting this
Students typically perform this experiment individually. ZnO wavelength to energy. Next, the particle diameter is determined
nanocrystals are formed through the reaction of zinc acetate using the following empirical relationship:11
281 dx.doi.org/10.1021/ed300693d | J. Chem. Educ. 2014, 91, 280−282
Journal of Chemical Education
⎛ 1240 ⎞ AUTHOR INFORMATION
⎜ − a⎟D2 + cD + b = 0
⎝ λhalf ⎠ (5)
where D is the diameter of the particles in angstroms (Å). The
empirical constants in eq 5 are taken from the literature: a =
3.301, b = −294.0, and c = −1.09.11 With the constants and λhalf
values, the quadratic equation is solved to determine D. With
particle diameters in hand, a plot of band-gap energy versus
(radius)−2, or (D/2)−2, is constructed (Figure 2). The
prediction of the particle-in-a-sphere model is that the band
gap of the ZnO nanoparticle scale as R−2, and the data are in
excellent agreement with this prediction.
Figure 2. Experimental (eq 5; diamond) and theoretical (eq 4; square)
ZnO band-gap energy versus particle size. Error bars for experimental
values lie within the points. Both experiment and theory demonstrate
the expected linear relationship between band-gap energy and R−2,
where R is particle radius. The data presented in the figure were
acquired by a student and represent the quality of data routinely
acquired.
The experimental results can also compared to the
theoretical predictions of eq 4 using values for the various
constants for ZnO obtained from the literature:13 Ebulk
bg = 3.4 eV,
m*e = 0.25me = 0.25(9.1 × 10−31 kg), m*h = 0.45me = 0.45(9.1 ×
10−31 kg), and ε = 3.7. With these values, the predicted
dependence of Ebg on particle radius is calculated and plotted
versus R−2 (Figure 2). The agreement between experiment and
theory is modest for smaller particles, but improves with
particle size. For the smallest particles (R = 10.4 Å), the
predicted band gap is 4.6 eV versus the experimental value of
4.2 eV, a ∼10% difference in energy. Similar limitations of the
theoretical model in describing the variation of the particle
band-gap energy with particle size have been noted and
attributed to modeling the nanocrystal environment as a
spherical dielectric continuum.12
■
SUMMARY
Over 200 students have successfully performed this experiment
over the past 5 years. This laboratory is typically performed
after coursework in quantum mechanics to reinforce concepts
encountered in a more theoretical context.
■
*
ASSOCIATED CONTENT
S Supporting Information
A complete description of the laboratory including instructions
for students performing the lab. This material is available via
the Internet at http://pubs.acs.org.
282
■
Laboratory Experiment
Corresponding Author
*E-mail: pjreid@uw.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
(PJR: DMR 1005819, DRG: CHE 1151726).
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